Hair cosmetic composition

ABSTRACT

The present invention provides a hair cosmetic composition containing the following components (A), (B), (C), and (D): 
     (A) an organic solvent, 
     (B) a naphthalene sulfonic acid and/or a benzophenone sulfonic acid, 
     (C) an anionic surfactant and/or an amphoteric surfactant, and 
     (D) an oily agent. 
     The hair cosmetic composition of the invention imparts satisfactory firmness/elasticity to hair in a short time, holds the firmness/elasticity for a long time, and provides the hair with excellent conditioning effects.

This application is a 371 of PCT/JP95/0084.

TECHNICAL FIELD

The present invention relates to a hair cosmetic composition whichimparts satisfactory firmness/elasticity to hair fibers in a short time,which holds the firmness/elasticity for a long time, and which at thesame time provides the hair with conditioning effects.

BACKGROUND ART

Not a few complaints about the hair are caused from the low elasticityof hair fibers such as lack of firmness/elasticity and less volume. Inorder to meet the needs of people having such complaints, a variety ofhair treatment compositions have heretofore been proposed which containcomponents for providing firmness/elasticity and components withconditioning effects. A majority of them exhibit their effects when theyare adsorbed onto the surfaces of hair fibers, but the adsorbedcompositions are rinsed off upon shampooing. Therefore, repeatedtreatments are needed, which is not convenient. Separately, attemptshave been made to obtain an effect by permeating a hair treatmentcomposition into hair fibers. However, the permeability of thecomposition is poor and requires a prolonged time for treatment whileproducing only an insufficient effect.

Hair treatment compositions proposed by EP-A-0529437 comprise an organicsolvent and an aromatic sulfonic acid. Although this composition impartsfirmness/elasticity to hair fibers in a short time and the effects ofthe composition are long-lasting, the conditioning effects of thecomposition such as providing moistness, smoothness, etc. to hair fibersare still unsatisfactory.

Accordingly, hair cosmetic compositions capable of impartingfirmness/elasticity to hair fibers in a short time, holding thefirmness/elasticity for a long time, and providing the hair withsatisfactory conditioning effects are still desired.

DISCLOSURE OF THE INVENTION

Accordingly, the present invention provides a hair cosmetic compositionwhich comprises the following components (A), (B), (C), and (D):

(A) an organic solvent,

(B) a naphthalene sulfonic acid and/or a benzophenone sulfonic acid,

(C) an anionic surfactant and/or an amphoteric surfactant, and

(D) an oily agent.

According to the present invention, satisfactory firmness/elasticity canbe given to hair fibers through a short-term treatment due to theincorporation of an organic solvent, a naphthalene sulfonic acid and/ora benzophenone sulfonic acid, an anionic surfactant and/or an amphotericsurfactant, and an oily agent, and the effects obtained arelong-lasting. In addition, conditioning effects can also be given to thehair.

BEST MODE FOR CARRYING OUT THE INVENTION

The organic solvent which is used in the present invention as component(A) is compatible with water. Examples of the organic solvent (A)include the compounds of the following formula (1), N-alkylpyrrolidonesof the following formula (2), and C1-C4 alkylene carbonates. ##STR1##wherein R¹ represents hydrogen, lower alkyl, or a group ##STR2##(wherein R² represents hydrogen, methyl, or methoxy, R³ represents adirect bond or a C1-C3 saturated or unsaturated divalent hydrocarbongroup), Y and Z each represents hydrogen or hydroxy, p, q, and r areintegers of from 0 to 5, with the exception of the cases where p═q═r═0and Z═H; and p═q═r═0, R¹ =H, and Z═OH. ##STR3## wherein R⁴ representsC1-C18 linear or branched alkyl.

Among the above-described species of component (A), the aromaticalcohols of the following formula (3) are especially preferred. ##STR4##wherein R⁵ is hydrogen or methyl, s is an integer from 0 to 5 inclusive,and R² and R³ have the same meaning as described above with theexception that R³ is not a direct bond if s is equal to 0.

Specific examples of the organic solvent (A) include ethanol,isopropanol, n-propanol, n-butanol, isobutanol, ethylene glycol,propylene glycol, 1,3-butanediol, benzyl alcohol, cinnamyl alcohol,phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, phenoxy isopropanol, 2-benzyloxyethanol, methyl carbitol, ethylcarbitol, propyl carbitol, butyl carbitol, triethylene glycolmonoethylether, triethylene glycol monobutyl ether, glycerol,N-methylpyrrolidone, N-octylpyrrolidone, N-laurylpyrrolidone, ethylenecarbonate(1,3-dioxolan-2-one), propylenecarbonate(4-methyl-1,3-dioxolan-2-one), butylenecarbonate(4-ethyl-1,3-dioxolan-2-one), etc. They are used singly or incombinations of two or more.

Of these compounds, aromatic alcohols of formula (3) are especiallypreferred. Specifically, benzyl alcohol, cinnamyl alcohol, phenethylalcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxy ethanol,phenoxy isopropanol, 2-benzyloxyethanol are preferred with benzylalcohol, p-methylbenzyl alcohol, 2-benzyloxyethanol, phenoxy ethanol,and phenoxy isopropanol being particularly preferred.

The organic solvent (A) is preferably incorporated in the hair cosmeticcomposition of the invention in an amount of from 0.5 to 50% by weight(hereinafter simply referred to as %) based on the total amount of thecomposition. If the amount of the organic solvent (A) is in the rangefrom 2 to 30%, or particularly from 5 to 25%, prominent effects can beobtained with favorable sensation and thus preferable. The proportionbetween water and the organic solvent depends on the solubility of thesolvent in water. Generally, the proportion of the amount of the organicsolvent to that of water is preferably from 10:90 to 50:50.

Of the species of component (B) which are used in the present invention,examples of the naphthalene sulfonic acid include the compoundsrepresented by the following formula (4): ##STR5## wherein one or moreof A¹ to A⁸ represent a sulfonic group or a salt thereof, and theremaining group(s) represent(s) hydrogen, halogen, hydroxy, nitro,carboxy, lower alkoxycarbonyl, alkyl, alkenyl, lower alkoxy, formyl,acyl, phenylazo or substituted phenylazo, or a group ##STR6## wherein R'and R" represent hydrogen, lower alkyl, lower alkenyl, phenyl, benzyl,or acyl.

In the above formula (4), examples of the alkyl include C1-C18 alkyl,examples of the alkenyl include C2-C18 alkenyl, examples of the loweralkyl and lower alkoxy include those of C1-C6, and examples of the loweralkenyl include C2-C6 alkenyl. Examples of the acyl include C2-C6alkanoyl; examples of substituted or unsubstituted phenylazo includephenylazo, carboxyphenylazo, etc; examples of the halogen includefluorine, chlorine, bromine, and iodine. It is preferred that one or twoof the A¹ to A⁸ of the formula (4) be sulfonic acid or a salt thereof.Examples of the salt of sulfonic acid include alkaline metal salts suchas a sodium salt, potassium salt, etc., ammonium salts, and quaternaryammonium salts.

Specific examples of the naphthalene sulfonic acid include 1- or 2-naphthalene sulfonic acid, 1,3-naphthalenedisulfonic acid,1,7-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid,1,5-naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid,1,3,6-naphthalene-trisulfonic acid, 1-naphthol-2-sulfonic acid,1-naphthol-4-sulfonic acid, 2-naphthol-6-sulfonic acid,2-naphthol-7-sulfonic acid, 1-naphthol-3,6-disulfonic acid,2-naphthol-3,6-disulfonic acid, 2-naphthol-6,8-disulfonic acid,2,3-dihydroxynaphthalene-6-sulfonic acid,1,7-dihydroxy-naphthalene-3-sulfonic acid, chromotoropic acid(4,5-dihydroxynaphthalene-2,7-disulfonic acid),3,6-dihydroxynaphthalene-2,7-disulfonic acid, S acid(1-amino-8-naphthol-4-sulfonic acid), gamma acid(2-amino-8-naphthol-6-sulfonic acid), J acid(2-amino-5-naphthol-7-sulfonic acid), H acid(1-amino-8-naphthol-3,6-disulfonic acid),7-amino-1,3-naphthalenedisulfonic acid, 1-amino-2-naphthol-4-sulfonicacid, 1-naphthylamine-4-sulfonic acid, Broenner's acid(2-naphthylamine-6-sulfonic acid), Cleve's acid(1-naphthylamine-7-sulfonic acid), 2-naphthylamine-1-sulfonic acid,1-naphthylamine-6-sulfonic acid, 1-naphthylamine-8-sulfonic acid,4-amino-5-hydroxy-8-phenylazo-2,7-naphthalenedisulfonic acid,4-amino-8-(4-carboxyphenylazo)-5-hydroxy-2,7-naphthalenedisulfonic acid,6-amino-4-hydroxy-3-phenylazo-2-naphthalenesulfonic acid,4-amino-8-(4-carboxyphenylazo)-5-hydroxy-1-naphthalenesulfonic acid,7-amino-4-hydroxy-1-phenylazo-2-naphthalenesulfonic acid,8-amino-5-(4-carboxyphenylazo)-2-naphthalenesulfonic acid,4-amino-3-(4-carboxyphenylazo)-5-hydroxy-1-naphthalenesulfonic acid,6-amino-4-hydroxy-5-phenylazo-2-naphthalenesulfonic acid,2,7-diamino-1-naphthol-3-sulfonic acid,7,8-diamino-1-naphthol-3-sulfonic acid, naphthalenesulfonic acid -formalin polycondensation product (weight-average degree ofpolycondensation: 2-100), 6-methyl-2-naphthalenesulfonic acid,4-ethyl-1-naphthalenesulfonic acid, 5-isopropyl-1-naphthalenesulfonicacid, 5-butyl-2-naphthalenesulfonic acid, and their salts. Of these,particularly preferred are 1-naphthalenesulfonic acid,2-naphthalenesulfonic acid, 1,5-naphthalenedisulfonic acid,2,6-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid,1,3-naphthalenedisulfonic acid, H acid(1-amino-8-naphthol-3,6-disulfonic acid), 1,3,6-naphthalenetrisulfonicacid, chromotoropic acid, and naphthalenesulfonic acid - formalinpolycondensation product (weight-average degree of polycondensation:2-100), and their salts.

Of the species of component (B), examples of the benzophenonesulfonicacid include those of the following formula (5): ##STR7## wherein one ormore of A⁹ to A¹⁸ represent a sulfonic group or a salt thereof, and theremaining group(s) represent(s) hydrogen, halogen, hydroxy, carboxy,lower alkyl, lower alkenyl, lower alkoxy, or acyl.

In the above formula (5), the lower alkyl and the lower alkoxy includethose having 1 to 6 carbon atoms; and the lower alkenyl includes thosehaving 2 to 6 carbon atoms. Examples of the acyl include a C2-C6alkanoyl. Examples of the halogen include fluorine, chlorine, bromine,and iodine. It is particularly preferred that one or two of the A⁹ toA¹⁸ of the formula (5) be sulfonic acid or a salt thereof. Examples ofthe salt of sulfonic acid include alkaline metal salts such as a sodiumsalt, potassium salt, etc., alkaline earth metal salts such as a calciumsalt, ammonium salts, and quaternary ammonium salts.

Specific examples of the benzophenonesulfonic acid includeoxybenzonesulfonic acid, dihydroxydimethoxy-benzophenonedisulfonic acid,dihydroxy-dimethoxybenzophenonesulfonic acid,dihydroxy-dimethoxybenzophenonedisulfonic acid,o-chlorobenzo-phenonesulfonic acid, p-chlorobenzophenone-sulfonic acid,4,4'-dichlorobenzophenonesulfonic acid, 2,4-dichlorobenzophenonesulfonicacid, 2,4-dichlorobenzophenonesulfonic acid,2-hydroxybenzophenonesulfonic acid, 4-hydroxybenzophenonesulfonic acid,2-aminobenzophenonesulfonic acid, 4-aminobenzophenonesulfonic acid,2-methylbenzophenonesulfonic acid, 4-methoxybenzophenonesulfonic acid,4,4'-dimethylbenzophenonesulfonic acid,4,4'-dimethoxybenzophenonesulfonic acid,4-chloro-4'-hydroxybenzophenonesulfonic acid, and their salts. Of these,particularly preferred are oxybenzonesulfonic acid,dihydroxymethoxybenzophenonedisulfonic acid,dihydroxydimethoxybenzophononesulfonic acid,dihydroxydimethoxybenzophenonedisulfonic acid, and their salts.

The naphthalenesulfonic acids and the benzosulfonic acids, which arecomponent (B), are used singly or in combinations of two or more. Theyare preferably incorporated in the hair cosmetic composition of theinvention in an amount from 0.1 to 10% by weight based on the totalamount of the composition. If the amount is in the range from 0.5 to 5%,or particularly from 1.0 to 3.0%, excellent firmness/elasticity can beimparted to the hair without impeding the feel to the touch of the hair,and thus preferable.

Of the species of component (C) which are used in the present invention,examples of the anionic surfactant include the following compounds.

(1) Linear or branched alkylbenzene sulfonates having an alkyl groupcontaining 10 to 16 carbon atoms on average.

(2) Alkyl or alkenyl ether sulfates having a linear or branched alkyl oralkenyl group containing 10 to 20 carbon atoms on average and apolyether chain to which 0.5 to 8 moles on average of ethylene oxide,propylene oxide, butylene oxide, or a combination of two or more ofthese is added per 1 molecule of sulfate.

(3) Alkyl or alkenyl sulfates having an alkyl or alkenyl groupcontaining 10 to 20 carbon atoms on average.

(4) Olefin sulfonates having 10 to 20 carbon atoms on average permolecule.

(5) Alkane sulfonates having 10 to 20 carbon atoms on average permolecule.

(6) Saturated or unsaturated fatty acid salts having 10 to 24 carbonatoms on average per molecule.

(7) Alkyl or alkenyl ether carboxylates having an alkyl or alkenyl groupcontaining 10 to 20 carbon atoms on average and a polyether chain towhich 0.5 to 8 moles on average of ethylene oxide, propylene oxide,butylene oxide, or a combination of two or more of these is added per 1molecule of carboxylate.

(8) Alpha-sulfofatty acid salts or esters having an alkyl or alkenylgroup containing 10 to 20 carbon atoms on average per molecule.

(9) N-acyl amino acid-type surfactants having a C8-C24 acyl group, afree carboxylic residue, or a sulfonic residue.

(10) Phosphoric mono- or di- ester-type surfactants having C8-C24 alkylor alkenyl, or their ethoxylates.

(11) Sulfosuccinic esters derived from a higher aliphatic amide or aC8-C22 higher alcohol or its ethoxylates.

(12) Sulfonic acid salts of C8-C20 higher fatty aid monoethanolamides,diethanolamides or their ethoxylates.

(13) Sulfonic acid salts of C8-C20 monoglycerides.

(14) Salts of C8-C20 higher fatty acids and isethionic acid.

Of the species of component (C), examples of the amphoteric surfactantinclude the following compounds.

(1) Imidazolines having C8-C24 alkyl, alkenyl or acyl, and of an alpha-adduct type, secondary amide type, or a tertiary amide type.

(2) Carbobetaines, amidebetaines, sulfobetaines, hydroxysulfobetaines,and amidesulfobetaines having C6-C24 alkyl, alkenyl or acyl.

(3) Amineoxides having C6-C24 alkyl or alkenyl.

Among the above surfactants, the compounds (a) to (f) below areparticularly preferred.

(a) N-acyl-L-glutamic acids and their salts represented by the followingformula (6): ##STR8## wherein R⁶ is C12-C18 linear or branched alkyl oralkenyl, X₁ and X₂ are hydrogen, potassium, sodium, or a triethanolaminesalt, with X₁ and X₂ being not necessarily identical.

(b) N-acyl-N-methyl-beta-alanines and their salts represented by thefollowing formula (7): ##STR9## wherein R⁶ has the same meaning asdefined above, X is hydrogen, potassium, sodium, or a triethanolaminesalt.

(c) Aminoalkyltaurinic acids and their salts represented by thefollowing formula (8): ##STR10## wherein R⁶ and X have the same meaningas defined above. (d) Amide ether sulfates and their salts representedby the following formula (9): ##STR11## wherein R⁶ is C12-C18 linear orbranched alkyl or alkenyl, R⁷ is C1-C3 linear alkyl, (A.O.)_(n) is 1 to5 moles on average (=n) of ethylene oxide, propylene oxide, or butyleneoxide (A.O.) which has been added, and R⁶ and X have the same meaning asdefined above.

(e) Monoalkyl or dialkyl phosphoric acids and their salts represented bythe following formula (10): ##STR12## wherein R⁸ is C12-C18 linear orbranched alkyl or alkenyl, and R⁶ and X have the same meaning as definedabove (if R⁸ is hydrogen, the formula (10) represents monoalkylphosphoric acids and their salts).

(f) Secondary amide- or tertiary amide-type imidazoline amphotericsurfactants and their salts represented by the following formulas (11),(12), and (13): ##STR13## wherein R⁹ is C7-C18 linear or branched alkylor alkenyl, and X has the same meaning as defined above; ##STR14##wherein R⁹ and X have the same meaning as defined above; ##STR15##wherein R⁹ and X have the same meaning as defined above. (g)Carbobetaine-type, sulfobetaine-type, and hydroxysulfobetaine-typeamphoteric surfactants represented by the following formulas (14) and(15): ##STR16## wherein R¹⁰ is C6-C24 alkyl, alkenyl, or acyl; ##STR17##wherein Y is hydrogen or hydroxyl, and R¹⁰ has the same meaning asdefined above.

These anionic and amphoteric surfactants are used singly or incombinations of two or more. They are preferably incorporated in anamount of from 0.1 to 25% based on the total amount of the composition.If the amount falls in a range from 0.5 to 15%, and in particular from1.0 to 10%, excellent feel to the touch can be obtained and thuspreferable.

Examples of the oily agent, component (D), include various oils and fatsand hydrocarbons which are either liquid or solid.

Examples of the oils and fats include C12-C30 saturated or unsaturatedalcohols; ethers of these alcohols and polyhydric alcohols; esters ofthese alcohols and C1-C11 fatty acids; C12-C30 saturated or unsaturatedfatty acids; esters of these fatty acids and monohydric or polyhydricalcohols; amides of these fatty acids and amines; sterols; squalenes;phospholipids; glycolipids; oils or fats of animal origin; and oils orfats of vegetable origin.

Examples of the C12-C30 saturated or unsaturated alcohols includen-dodecal, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleylalcohol, octyldodecanol, behenyl alcohol, ceryl alcohol, myricylalcohol, caranabyl alcohol, arachin alcohol, and the like. Examples ofthe polyhydric alcohols which can form ethers with these alcoholsinclude glycerol and polyalkylene glycol, and examples the formed ethersinclude alpha-monoisostearyl glyceryl ether, polyoxyethylenepolyoxypropylene stearyl ether, polyoxyethylene cetyl ether,polyoxyethylene octyldodecyl ether, and the like. Examples of the estersof these alcohols and C1-C11 fatty acids include cetyl 2-ethylhexanoate,diisostearyl malate, and the like.

Examples of the C12-C30 saturated or unsaturated fatty acids includelauric acid, myristic acid, 18-methyleicosanoic acid, palmitic acid,stearic acid, isostearic acid, behenic acid, cerotic acid, palm oilfatty acid, oleic acid, etc. Examples of the monohydric or polyhydricalcohols which can form esters with these fatty acids include theaforementioned C12-C30 saturated or unsaturated alcohols, glycerols,sterols, and fat-soluble vitamins, and examples of the formed estersinclude oleic monoglycerides, palmitic monoglycerides, behenicmonoglycerides, myristic monoglycerides, isostearic monoglycerides,isostearic diglycerides, polyoxyethylene glyceryl monoisostearates,isopropyl myristates, cholesteryl ester isostearates, dipentaerythritolfatty acid esters. Examples of the amides of these fatty acids andamines include aliphatic dialkylaminoalkylamides (long chainamideamines), and specifically, diethylaminoethylamide stearate(Amideamine S by Kao Corp.).

Specific examples of the phospholipids include soybean phospholipids,and specific examples of the glycolipids include sophorose lipids(Glycolipid PSL by Kao Corp.). Specific examples of the oils and fats ofanimal or vegetable origin include mink oil, olive oil (the majorcomponent is glycerol oleate), beeswax (the major component is myricylalcohol palmitate), palm oil (the major component is glycerolmyristate), whale wax (the major component is ceryl alcohol palmitate),and lanolin.

Examples of the hydrocarbons include Vaseline, liquid paraffin, solidparaffin, etc.

Of these oily agents, especially preferred are higher alcohols havingC12-C26 linear or branched alkyl or alkenyl groups.

These oily agents are used singly or in combinations of two or more.They are preferably incorporated in an amount of from 1 to 25% based onthe total amount of the composition. If the amount falls in a range offrom 3 to 20%, and in particular from 5 to 15%, remarkably satisfactoryresults can be obtained with excellent feel to the touch of the hair andthus preferable.

When cationic polymers are incorporated into the hair cosmeticcomposition of the present invention, even more excellent conditioningeffects can be obtained without affecting the capability of impartingfirmness/elasticity to the hair.

Examples of the cationic polymers include polymers or copolymers ofdimethyldiallylammonium chloride; polymers or copolymers ofmethacrylamide alkyl trimethyl ammonium; cationic cellulose;amino-modified silicone polymers.

The unit structure of the polymers of dimethyldiallyl ammonium chlorideis represented by the following formula (16). Preferable examples ofmonomers which form copolymers along with dimethyldiallylammoniumchloride include acrylates, acrylamides, hydroxyethylcellulose, etc.##STR18##

Specifically, mention may be given to a copolymer ofdimethyldiallylammonium chloride and hydroxyethylcellulose which isregistered under the name, Polyquaternium-4, in a dictionary of CTFA(The Cosmetic, Toiletry and Fragrance Association, Inc.); a polymer ofdimethyldiallylammonium chloride known as Polyquaternium-6; a copolymerof dimethyldiallylammonium chloride with acrylic amide known asPolyquaternium-7; a copolymer of dimethyldiallylammonium chloride withsodium acrylate known as Polyquaternium-22; and a threecomponent-copolymer of dimethyldiallylammonium chloride/acrylicamide/sodium acrylate known as Polyquaternium-39.

The unit structure of the polymers of methacrylamide alkyl trimethylammonium is represented by the following formula (17). Among themonomers which form copolymers along with methacrylamide alkyl trimethylammonium, vinylpyrrolidone is particularly preferred. ##STR19## whereinm is an integer of from 1 to 6, and A⁻ represents an anion).

Specifically, mention may De given to a copolymer of an ethyl sulfuricsalt of quaternarized dimethylaminoethyl methacrylate andvinylpyrrolidone which is registered under the name, Polyquaternium-11,in the dictionary of CTFA; a copolymer of methacrylamide propyltrimethyl ammonium with vinylpyrrolidone known as Polyquaternium-28; anda methacrylamide propyl trimethyl ammonium polymer.

Examples of the cationic cellulose include compounds having the unitstructure represented: by the following formula (18): ##STR20## wherein1 is an integer of from 0 to 10 (preferably from 0 to 5), R¹¹ is C1-C18alkyl, and A⁻ is an anion.

Specifically, mention may be given to hydroxyethylcellulose registeredunder the name, Polyquaternium-10, in the dictionary of CTFA; and2-hydroxypropyl triethyl ammonium chloride ether.

Examples of the amino-modified silicone polymers include polymers of anorganosiloxane having at least one aminoalkyl group in the molecule.

The organosiloxane generally contains a methyl group as a functionalgroup in addition to the aminoalkyl group. However, the functional groupis not limited only to methyl, and other functional groups may becontained including alkyl groups such as ethyl, propyl, etc.; alkenylgroups such as vinyl, allyl, etc.; aryl groups such as phenyl, naphthyl,etc.; cycloalkyl groups such as cyclohexyl; and other groups such ashydroxy, hydroxyalkyl, hydroxyalkylene, and polyoxyalkylene, etc.

Typical examples of the aminoalkyl groups contained in theamino-modified silicone polymers are those represented by the followingformulas (19) or (20): ##STR21## wherein R¹² represents a divalenthydrocarbon group, R¹³ represents ##STR22## R¹⁴ and R¹⁵ representhydrogen or a monovalent hydrocarbon group, and d and e are integers offrom 0 to 6. ##STR23## wherein R¹² represents a divalent hydrocarbongroup, R¹³ represents ##STR24## R¹⁴ represents hydrogen or a monovalenthydrocarbon group, d and e are integers of from 0 to 6, and Z⁻ is ahalogen ion or an organic anion.

Examples of the divalent hydrocarbon group represented by R¹² informulas (19) and (20) include C1-C6 alkylene groups such as methylene,ethylene, propylene, butylene, and --CH₂ CH(CH₃)CH₂ --; and C7-C10alkylenearylene groups such as --(CH₂)₂ --C₆ H₄ --. Of these, alkylenegroups, particularly propylene, are preferred. Examples of themonovalent hydrocarbon group represented by R¹⁴ and R¹⁵ include C1-C18alkyl or aryl groups such as methyl, ethyl, propyl, hexyl, and phenyl.Both of the groups R¹⁴ and R¹⁵ may be hydrogen or a monovalenthydrocarbon group. Alternatively, they may be different in such as amanner that R¹⁴ is hydrogen and R¹⁵ is a monovalent hydrocarbon group.Preferable values of d and e are such that d=0 and e=1.

Typically, the hydroxyalkyl group is represented by the followingformula: ##STR25## wherein R¹² has the same meaning as defined above.

Typically, the oxyalkyene group and polyoxyalkylene group arerepresented by the following formula (21): ##STR26## wherein R¹² has thesame meaning as defined above, f is an integer 0 or 1, g is an integerfrom 1 to 100 inclusive, and h is an integer from 1 to 5 inclusive.

Among the oxyalkylene group and polyoxyalkylene group represented by thefollowing formula (21), preferable ones are those in which f is equal to1, g is an integer of from 3 to 70, and h is 2 or 3. Those in which h is2 or 3 may be linked in blocks or at random, and the same applies toother cases where h is an integer other than 2 or 3.

Typically, the amino-modified silicone polymers are represented by thefollowing formulas (22) or (23): ##STR27## wherein R¹⁶ represents methylor hydroxy, R¹⁷ represents methyl or hydrogen, R¹⁸ represents theaforementioned aminoalkyl (formula (19) or (20)), R¹⁹ representshydroxy, hydroxyalkyl, oxyalkylene, or polyoxyalkylene, and j and k areintegers which vary depending on the molecular weight. ##STR28## whereinR¹⁶, R¹⁷, R¹⁸, and R¹⁹ have the same meaning as defined above, and i, j,and k are integers which vary depending on the molecular weight.

Of the above-mentioned amino-modified silicone polymers, particularlypreferable ones are those represented by the following formula (24):##STR29## wherein R²⁰, j, and k have the same meaning as defined above.

Typical examples of the amino-modified silicone polymers in the presentinvention are those represented by the following formula (25) and havingan average molecular weight of from about 3,000 to 100,000. This polymeris described in the aforementioned dictionary of CTFA (3rd ed.) underthe name, Amodimethicone. ##STR30## wherein s and t are integers whichvary depending on the molecular weight ranging from 3,000 to 100,000.

The above-described cationic polymers are used singly or in combinationsof two or more. They are preferably incorporated in an amount of from0.05 to 10% based on the total amount of the composition. If the amountfalls in a range of from 0.05 to 5%, particularly from 0.05 to 3%, aneffect providing excellent feel to the touch of the hair is expectedwithout impeding the firmness/elasticity-imparting effect and thuspreferable.

The pH of the hair cosmetic composition of the present invention ispreferably adjusted to fall in the range from 2 to 5, more preferablyfrom 2.5 to 4.5, by adding thereto a compound capable of forming abuffer system such as an organic carboxylic acid or a salt thereof inorder to allow the hair fibers sufficiently to swell for acceleratingpermeation of the firmness/elasticity-imparting components,naphthalenesulfonic acids and/or benzophenonesulfonic acids into thehair fibers.

The compounds which are capable of forming the buffer system includeorganic carboxylic acids such as citric acid, glycolic acid, succinicacid, tartaric acid, lactic acid, acetic acid, fumaric acid, malic acid,levulinic acid, butyric acid, valeric acid, oxalic acid, maleic acid,phthalic acid, mandelic acid, isethionic acid and their salts.Preferable salts of these carboxylic acids include sodium salts,potassium salts, and ammonium salts.

These carboxylic acids are used singly or in combinations of two ormore. They are incorporated in such amounts that make the pH of thecomposition to fall within the above-indicated pH range. Generally, theyare incorporated from 0.3 to 50%, especially from 0.5 to 30%, based onthe total amount of the composition.

If necessary, the hair cosmetic composition of the present invention mayfurther contain optional components as long as the effects of theinvention are not impeded. The optional components include thickenerssuch as hydroxyethylcellulose, anionic, amphoteric, and other types ofsetting polymers, perfumes, pearl-hue imparting agents, colorants, UVabsorbers, antioxidants, preservatives, etc. In order to further improvefeel to the touch of the hair, it is possible to incorporate siliconederivatives such as dimethylpolysiloxanes, polyether-modified silicones,alkyl-modified silicones, alkoxy-modified silicones, and aliphaticmodified silicones.

In the hair cosmetic composition of the present invention, the balanceof the above-described components is water.

The hair cosmetic composition of the present invention can be preparedby a method generally known in the art into various products such ashair treatments, hair conditioners, and other products which are usedoutside the bath such as hair treatment foams, hair setting foams, hairsprays, and hair creams.

In use, the hair cosmetic composition of the present invention may, forexample, be applied to hair fibers in the bath, be allowed to stand for5 to 30 minutes, and then rinsed off. During the standing period, thehair may be heated to a suitable temperature which is preferably from30° to 50° C. When the hair cosmetic composition of the invention isused outside the bath, it is applied to the hair (either dry hair or wethair after shampooing) and is brought into full contact with the entiresurfaces of the hair fibers.

EXAMPLES

The present invention will next be described by way of examples, whichshould not be construed as limiting the invention.

Examples 1 to 10 and Comparative Examples 1 to 8:

The hair cosmetic compositions shown in Tables 1, 2, 3, 4, and 5 wereprepared, and the hair treatment effects of the compositions wereinvestigated.

(1) The hair used in the test:

Hair fiber samples of Japanese women which had not undergone any beautytreatments such as cold perming or bleaching.

(2) Evaluation method:

Hair fiber samples each weighing 8 g were provided. Each sample wasdivide into two. To one half, an invention composition (or a comparativecomposition) in a solution of 1:1 was applied, and was allowed to standat room temperature for 10 minutes. Subsequently, the composition wasrinsed off with running water, after which the hair was dried with ahair drier or similar means. The resulting sample represented a treatedsample. The other half, which was not treated with any compositionsrepresented a non-treated sample. 10 expert panelists compared each pairin a side-by-side manner with respect to the firmness/elasticity,moistened feel to the touch of the hair, and smoothness to the touch ofthe hair. The evaluation of firmness/elasticity was repeated after thesample was shampooed twice. The evaluation standards were as follows:

Firmness/elasticity of the hair:

A: Remarkably excellent firmness/elasticity

B: Good firmness/elasticity

C: Slightly better firmness/elasticity than untreated hair

D: The same level as that of untreated hair.

Moistened feel to the touch of the hair:

A: Very moistened feel

B: Fairly moistened feel

C: Slightly moistened feel

D: The same level as that of untreated hair.

Smoothness to the touch of the hair:

A: Very smooth

B: Fairly smooth

C: Slightly smooth

D: The same level as that of untreated hair.

                  TABLE 1                                                         ______________________________________                                        Components (%)           Ex. 1   Ex. 2                                        ______________________________________                                        (1)  Benzyloxy ethanol       4.0     --                                       (2)  Benzyl alcohol          --      4.0                                      (3)  95% 8-Acetylated sucrose-modified ethanol                                                             10.0    10.0                                     (4)  Propylene glycol        3.0     3.0                                      (5)  2-Naphthalenesulfonic acid                                                                            --      2.0                                      (6)  Oxybenzonesulfonic acid*.sup.1                                                                        2.0     --                                       (7)  N-Palm oil aliphatic acyl-L-                                                                          8.0     --                                            glutamic acid triethanolamine (30%)*.sup.2                               (8)  2-Alkyl-N-carboxymethyl-N-                                                                            --      4.5                                           hydroxyethyl imidazolium betaine (58%)*.sup.3                            (9)  Cetanol                 5.0     4.0                                      (10) Behenyl alcohol         --      0.5                                      (11) alpha-Monoisostearylglyceryl ether*.sup.4                                                             1.5     1.5                                      (12) Polyoxyethylene cetyl ether (3 E.O.)                                                                  2.0     2.0                                      (13) Polyoxyethylene cetyl ether (40 E.O.)                                                                 2.0     2.0                                      (14) Hydroxyethylcellulose hydroxy-                                                                        --      --                                            propyl trimethylammonium chloride ether*.sup.5                           (15) Dimethyldiallyl ammonium chloride .                                                                   --      --                                            acrylic amide copolymer*.sup.6                                           (16) Aqueous citric acid solution (50%)                                                                    1.0     0.5                                      (17) NaOH (48%)              suitable                                                                      amount                                           (18) Purified water          balance                                          pH (adjusted with NaOH)  3.0     7.0                                          Firmness/elasticity (after dried):                                            Immediately after shampooing                                                                           A       B                                            After 2 shampooings      A       B                                            Feel to the touch of the hair during rinsing:                                 Smoothness               B       B                                            Moistness                B       B                                            Feel to the touch of the hair after drying:                                   Smoothness               A       A                                            Moistness                A       A                                            ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Components (%)           Ex. 3   Ex. 4                                        ______________________________________                                        (1)  Benzyloxy ethanol       4.0     --                                       (2)  Benzyl alcohol          --      4.0                                      (3)  95% 8-Acetylated sucrose-modified ethanol                                                             10.0    10.0                                     (4)  Propylene glycol        4.5     4.5                                      (5)  2-Naphthalenesulfonic acid                                                                            1.0     --                                       (6)  Oxybenzonesulfonic acid*.sup.1                                                                        1.0     2.0                                      (7)  N-Palm oil aliphatic acyl-L-                                                                          --      8.0                                           glutamic acid triethanolamine (30%)*.sup.2                               (8)  2-Alkyl-N-carboxymethyl-N-                                                                            4.5     --                                            hydroxyethyl imidazolium betaine (58%)*.sup.3                            (9)  Cetanol                 --      --                                       (10) Behenyl alcohol         --      --                                       (11) alpha-Monoisostearylglyceryl ether*.sup.4                                                             1.5     1.5                                      (12) Polyoxyethylene cetyl ether (3 E.O.)                                                                  2.0     2.0                                      (13) Polyoxyethylene cetyl ether (40 E.O.)                                                                 2.0     2.0                                      (14) Hydroxyethylcellulose hydroxy-                                                                        --      --                                            propyl trimethylammonium chloride ether*.sup.5                           (15) Dimethyldiallyl ammonium chloride .                                                                   --      --                                            acrylic amide copolymer*.sup.6                                           (16) Aqueous citric acid solution (50%)                                                                    1.0     0.5                                      (17) NaOH (48%)              suitable                                                                      amount                                           (18) Purified water          balance                                          pH (adjusted with NaOH)  3.0     7.0                                          Firmness/elasticity (after dried):                                            Immediately after shampooing                                                                           A       B                                            After 2 shampooings      A       B                                            Feel to the touch of the hair during rinsing:                                 Smoothness               B       B                                            Moistness                B       B                                            Feel to the touch of the hair after drying:                                   Smoothness               B       B                                            Moistness                B       B                                            ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Components (%)          Ex. 5  Ex. 6  Ex. 7                                   ______________________________________                                        (1)  Benzyloxy ethanol      4.0    4.0  --                                    (2)  Benzyl alcohol         --     --   4.0                                   (3)  95% 8-Acetylated sucrose-modified ethanol                                                            10.0   10.0 10.0                                  (4)  Propylene glycol       3.0    3.0  3.0                                   (5)  2-Naphthalenesulfonic acid                                                                           1.0    1.0  --                                    (6)  Oxybenzonesulfonic acid*.sup.1                                                                       1.0    1.0  2.0                                   (7)  N-Palm oil aliphatic acyl-L-                                                                         8.0    8.0  --                                         glutamic acid triethanolamine (30%)*.sup.2                               (8)  2-Alkyl-N-carboxymethyl-N-                                                                           --     --   4.5                                        hydroxyethyl imidazolium betaine (58%)*.sup.3                            (9)  Cetanol                5.0    5.0  4.0                                   (10) Behenyl alcohol        --     --   0.5                                   (11) alpha-Monoisostearylglyceryl ether*.sup.4                                                            1.5    1.5  1.5                                   (12) Polyoxyethylene cetyl ether (3 E.O.)                                                                 2.0    2.0  2.0                                   (13) Polyoxyethylene cetyl ether (40 E.O.)                                                                2.0    2.0  2.0                                   (14) Hydroxyethylcellulose hydroxy-                                                                       0.2    --   0.2                                        propyl trimethylammonium chloride ether*.sup.5                           (15) Dimethyldiallyl ammonium chloride .                                                                  0.2    --   0.2                                        acrylic amide copolymer*.sup.6                                           (16) Imidazolium methochloride .                                                                          --     0.4  --                                         vinyl pyrrolidone copolymer*.sup.7                                       (17) Aqueous citric acid solution (50%)                                                                   1.0    1.0  1.0                                   (18) NaOH (48%)             suitable amount                                   (19) Purified water         balance                                           pH (adjusted with NaOH) 3.0    3.0    7.0                                     Firmness/elasticity (after dried):                                            Immediately after shampooing                                                                          A      A      B                                       After 2 shampooings     A      A      B                                       Feel to the touch of the hair during rinsing:                                 Smoothness              A      B      A                                       Moistness               A      B      A                                       Feel to the touch of the hair after drying:                                   Smoothness              A      A      A                                       Moistness               A      A      A                                       ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                                                Ex.    Ex.    Ex.                                     Components (%)          8      9      10                                      ______________________________________                                        (1)  Benzyloxy ethanol      4.0    4.0  --                                    (2)  Benzyl alcohol         --     --   4.0                                   (3)  95% 8-Acetylated sucrose-modified ethanol                                                            10.0   10.0 10.0                                  (4)  Propylene glycol       3.0    3.0  3.0                                   (5)  2-Naphthalenesulfonic acid                                                                           2.0    2.0  --                                    (6)  Oxybenzonesulfonic acid*.sup.1                                                                       --     --   2.0                                   (7)  N-Palm oil aliphatic acyl-L-                                                                         --     --   8.0                                        glutamic acid triethanolamine (30%)*.sup.2                               (8)  2-Alkyl-N-carboxymethyl-N-                                                                           4.5    4.5  --                                         hydroxyethyl imidazolium betaine (58%)*.sup.3                            (9)  Cetanol                --     --   --                                    (10) Behenyl alcohol        --     --   0.5                                   (11) alpha-Monoisostearylglyceryl ether*.sup.4                                                            1.5    1.5  1.5                                   (12) Polyoxyethylene cetyl ether (3 E.O.)                                                                 2.0    2.0  2.0                                   (13) Polyoxyethylene cetyl ether (40 E.O.)                                                                2.0    2.0  2.0                                   (14) Hydroxyethylcellulose hydroxy-                                                                       0.2    --   0.2                                        propyl trimethylammonium chloride ether*.sup.5                           (15) Dimethyldiallyl ammonium chloride .                                                                  0.2    --   0.2                                        acrylic amide copolymer*.sup.6                                           (16) Imidazolium methochloride .                                                                          --     0.4  --                                         vinyl pyrrolidone copolymer*.sup.7                                       (17) Aqueous citric acid solution (50%)                                                                   1.0    1.0  0.5                                   (18) NaOH (48%)             suitable amount                                   (19) Purified water         balance                                           pH (adjusted with NaOH) 3.0    3.0    7.0                                     Firmness/elasticity (after dried):                                            Immediately after shampooing                                                                          A      A      B                                       After 2 shampooings     A      A      B                                       Feel to the touch of the hair during rinsing:                                 Smoothness              A      B      A                                       Moistness               A      B      A                                       Feel to the touch of the hair after drying:                                   Smoothness              B      B      B                                       Moistness               B      B      B                                       ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                                                 Comp.   Comp.                                        Components (%)           Ex. 1   Ex. 2                                        ______________________________________                                        (1)  Benzyloxy ethanol       --      --                                       (2)  Benzyl alcohol          --      4.0                                      (3)  95% 8-Acetylated sucrose-modified ethanol                                                             --      10.0                                     (4)  Propylene glycol        --      3.0                                      (5)  2-Naphthalenesulfonic acid                                                                            --      --                                       (6)  Oxybenzonesulfonic acid*.sup.1                                                                        2.0     --                                       (7)  N-Palm oil aliphatic acyl-L-                                                                          8.0     --                                            glutamic acid triethanolamine (30%)*.sup.2                               (8)  2-Alkyl-N-carboxymethyl-N-                                                                            --      4.5                                           hydroxyethyl imidazolium betaine (58%)*.sup.3                            (9)  Cetanol                 5.0     4.0                                      (10) Behenyl alcohol         --      0.5                                      (11) alpha-Monoisostearylglyceryl ether*.sup.4                                                             1.5     1.5                                      (12) Polyoxyethylene cetyl ether (3 E.O.)                                                                  2.0     2.0                                      (13) Polyoxyethylene cetyl ether (40 E.O.)                                                                 2.0     2.0                                      (14) Hydroxyethylcellulose hydroxy-                                                                        --      --                                            propyl trimethylammonium chloride ether*.sup.5                           (15) Dimethyldiallyl ammonium chloride .                                                                   --      --                                            acrylic amide copolymer*.sup.6                                           (16) Aqueous citric acid solution (50%)                                                                    1.0     1.0                                      (17) NaOH (48%)              suitable                                                                      amount                                           (18) Purified water          balance                                          pH (adjusted with NaOH)  3.0     3.0                                          Firmness/elasticity (after dried):                                            Immediately after shampooing                                                                           C       D                                            After 2 shampooings      D       D                                            Feel to the touch of the hair during rinsing:                                 Smoothness               B       B                                            Moistness                B       B                                            Feel to the touch of the hair after drying:                                   Smoothness               B       B                                            Moistness                B       B                                            ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                                                 Comp.   Comp.                                        Components (%)           Ex. 3   Ex. 4                                        ______________________________________                                        (1)  Benzyloxy ethanol       --      --                                       (2)  Benzyl alcohol          4.0     4.0                                      (3)  95% 8-Acetylated sucrose-modified ethanol                                                             10.0    10.0                                     (4)  Propylene glycol        3.0     4.5                                      (5)  2-Naphthalenesulfonic acid                                                                            --      --                                       (6)  Oxybenzonesulfonic acid*.sup.1                                                                        2.0     2.0                                      (7)  N-Palm oil aliphatic acyl-L-                                                                          --      8.0                                           glutamic acid triethanolamine (30%)*.sup.2                               (8)  2-Alkyl-N-carboxymethyl-N-                                                                            --      --                                            hydroxyethyl imidazolium betaine (58%)*.sup.3                            (9)  Cetanol                 5.0     --                                       (10) Behenyl alcohol         --      --                                       (11) alpha-Monoisostearylglyceryl ether*.sup.4                                                             1.5     --                                       (12) Polyoxyethylene cetyl ether (3 E.O.)                                                                  2.0     --                                       (13) Polyoxyethylene cetyl ether (40 E.O.)                                                                 2.0     --                                       (14) Hydroxyethylcellulose hydroxy-                                                                        --      --                                            propyl trimethylammonium chloride ether*.sup.5                           (15) Dimethyldiallyl ammonium chloride .                                                                   --      --                                            acrylic amide copolymer*.sup.6                                           (16) Aqueous citric acid solution (50%)                                                                    1.0     1.0                                      (17) NaOH (48%)              suitable                                                                      amount                                           (18) Purified water          balance                                          pH (adjusted with NaOH)  3.0     3.0                                          Firmness/elasticity (after dried):                                            Immediately after shampooing                                                                           A       A                                            After 2 shampooings      A       A                                            Feel to the touch of the hair during rinsing:                                 Smoothness               D       C                                            Moistness                C       D                                            Feel to the touch of the hair after drying:                                   Smoothness               D       C                                            Moistness                C       D                                            ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                                                 Comp.   Comp.                                        Components (%)           Ex. 5   Ex. 6                                        ______________________________________                                        (1)  Benzyloxy ethanol       --      --                                       (2)  Benzyl alcohol          --      4.0                                      (3)  95% 8-Acetylated sucrose-modified ethanol                                                             --      10.0                                     (4)  Propylene glycol        --      3.0                                      (5)  2-Naphthalenesulfonic acid                                                                            --      --                                       (6)  Oxybenzonesulfonic acid*.sup.1                                                                        2.0     --                                       (7)  N-Palm oil aliphatic acyl-L-                                                                          8.0     --                                            glutamic acid triethanolamine (30%)*.sup.2                               (8)  2-Alkyl-N-carboxymethyl-N-                                                                            --      4.5                                           hydroxyethyl imidazolium betaine (58%)*.sup.3                            (9)  Cetanol                 5.0     4.0                                      (10) Behenyl alcohol         --      0.5                                      (11) alpha-Monoisostearylglyceryl ether*.sup.4                                                             1.5     1.5                                      (12) Polyoxyethylene cetyl ether (3 E.O.)                                                                  2.0     2.0                                      (13) Polyoxyethylene cetyl ether (40 E.O.)                                                                 2.0     2.0                                      (14) Hydroxyethylcellulose hydroxy-                                                                        2.0     2.0                                           propyl trimethylammonium chloride ether*.sup.5                           (15) Dimethyldiallyl ammonium chloride .                                                                   0.2     0.2                                           acrylic amide copolymer*.sup.6                                           (16) Aqueous citric acid solution (50%)                                                                    1.0     0.5                                      (17) NaOH (48%)              suitable                                                                      amount                                           (18) Purified water          balance                                          pH (adjusted with NaOH)  3.0     3.0                                          Firmness/elasticity (after dried):                                            Immediately after shampooing                                                                           C       D                                            After 2 shampooings      D       D                                            Feel to the touch of the hair during rinsing:                                 Smoothness               A       A                                            Moistness                A       A                                            Feel to the touch of the hair after drying:                                   Smoothness               A       A                                            Moistness                A       A                                            ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                                                 Comp.   Comp.                                        Components (%)           Ex. 7   Ex. 8                                        ______________________________________                                        (1)  Benzyloxy ethanol       --      --                                       (2)  Benzyl alcohol          4.0     4.0                                      (3)  95% 8-Acetylated sucrose-modified ethanol                                                             10.0    10.0                                     (4)  Propylene glycol        3.0     4.5                                      (5)  2-Naphthalenesulfonic acid                                                                            --      --                                       (6)  Oxybenzonesulfonic acid*.sup.1                                                                        2.0     2.0                                      (7)  N-Palm oil aliphatic acyl-L-                                                                          --      8.0                                           glutamic acid triethanolamine (30%)*.sup.2                               (8)  2-Alkyl-N-carboxymethyl-N-                                                                            --      --                                            hydroxyethyl imidazolium betaine (58%)*.sup.3                            (9)  Cetanol                 5.0     --                                       (10) Behenyl alcohol         --      --                                       (11) alpha-Monoisostearylglyceryl ether*.sup.4                                                             1.5     --                                       (12) Polyoxyethylene cetyl ether (3 E.O.)                                                                  2.0     --                                       (13) Polyoxyethylene cetyl ether (40 E.O.)                                                                 2.0     --                                       (14) Hydroxyethylcellulose hydroxy-                                                                        0.2     0.2                                           propyl trimethylammonium chloride ether*.sup.5                           (15) Dimethyldiallyl ammonium chloride .                                                                   0.2     0.2                                           acrylic amide copolymer*.sup.6                                           (16) Aqueous citric acid solution (50%)                                                                    1.0     0.5                                      (17) NaOH (48%)              suitable                                                                      amount                                           (18) Purified water          balance                                          pH (adjusted with NaOH)  3.0     3.0                                          Firmness/elasticity (after dried):                                            Immediately after shampooing                                                                           A       A                                            After 2 shampooings      A       A                                            Feel to the touch of the hair during rinsing:                                 Smoothness               D       C                                            Moistness                C       D                                            Feel to the touch of the hair after drying:                                   Smoothness               C       C                                            Moistness                C       C                                            ______________________________________                                         Note)                                                                         *1: Uvinul MS40 (BASF JAPAN)                                                  *2: Amisoft CT12 (Ajinomoto)                                                  *3: Amphitol 20Y (Kao)                                                        *4: GE1S (Kao)                                                                *5: PolymerJR400 (Union Carbide)                                              *6: Merquat 2200 (Calgon)                                                     *7: Luviquat FC (BASF)                                                   

EXAMPLE 11

A hair treatment composition of the following formula was prepared by aroutine method. It had excellent properties in both thefirmness/elasticity of hair fibers and the conditioning effects(moistness, smoothness).

    ______________________________________                                        Formula                 (%)                                                   ______________________________________                                        (1)   2-Naphthalenesulfonic acid . Na                                                                     1.0                                               (2)   Oxybenzonesulfonic acid                                                                             1.0                                               (3)   95% 8-Acetylated sucrose-modified                                                                   10.0                                                    ethanol                                                                 (4)   Benzyloxy ethanol     3.0                                               (5)   Dimethyldiallyl ammonium chloride .                                                                 0.3                                                     acrylic amide copolymer                                                 (6)   Hydroxyethylcellulose hydroxypropyl-                                                                0.3                                                     trimethylammonium chloride ether                                        (7)   Aqueous citric acid solution (50%)                                                                  1.0                                               (8)   N-Palm oil aliphatic acyl-L-                                                                        3.0                                                     glutamic acid triethanolamine*.sup.1                                    (9)   Monolauryl phosphoric acid*.sup.2                                                                   2.5                                               (10)  Cetanol               5.0                                               (11)  Polyoxyethylene cetyl ether (40 E.O.)                                                               2.0                                               (12)  Aqueous NaOH solution (48%)                                                                         suitable amount for                                                           adjusting pH to 3.0                               (13)  Purified water        balance                                                 Total                 100                                               ______________________________________                                         Note)                                                                         *1: Amisoft LS11 (Ajinomoto)                                                  *2: MAP20H (Kao)                                                         

EXAMPLE 12

A hair treatment composition of the following formula was prepared by aroutine method. It had excellent properties in both thefirmness/elasticity of hair fibers and the conditioning effects.

    ______________________________________                                        Formula                 (%)                                                   ______________________________________                                        (1)   1-Naphthalenesulfonic acid . Na                                                                     2.0                                               (2)   95% 8-Acetylated sucrose-modified                                                                   5.0                                                     ethanol                                                                 (3)   Diethylene glycol monoethyl ether                                                                   5.0                                               (4)   Benzyl alcohol        4.0                                               (5)   Hydroxyethylcellulose hydroxypropyl-                                                                0.5                                                     trimethylammonium chloride ether                                        (6)   Aqueous citric acid solution (50%)                                                                  1.0                                               (7)   Lauryldimethylamine oxide (35%)*.sup.1                                                              1.0                                               (8)   Amideamino acid triethanolamine (34%)*.sup.2                                                        5.0                                               (9)   Cetanol               4.0                                               (10)  Behenyl alcohol       1.5                                               (11)  Polyoxyethylene cetyl ether (40 E.O.)                                                               2.0                                               (12)  Aqueous NaOH solution (48%)                                                                         suitable amount for                                                           adjusting pH to 3.5                               (13)  Purified water        balance                                                 Total                 100                                               ______________________________________                                         Note)                                                                         *1: Amphitol 20N (Kao)                                                        *2: Amphitol 20YN (Kao)                                                  

EXAMPLE 13

A hair foam composition of the following formula was prepared by aroutine method. It had excellent properties in both thefirmness/elasticity of hair fibers and the conditioning effects(moistness, smoothness).

    ______________________________________                                        Formula                 (%)                                                   ______________________________________                                        (1)  Oxybenzonesulfonic acid                                                                              0.5                                               (2)  95% 8-Acetylated sucrose-modified                                                                    10.0                                                   ethanol                                                                  (3)  Amideamino acid triethanolamine 24%                                                                  0.5                                                    (= Amphitol 20Y-N (Kao))                                                 (4)  Polyoxyethylene-sec-tetradecyl                                                                       1.0                                                    ether (9 E.O.)*.sup.1                                                    (5)  N-methacryloylethyl-N,N-dimethyl-                                                                    1.0                                                    ammonium . alpha-N-methylcarboxybetaine .                                     butyl methacrylate copolymer*.sup.2                                      (6)  Dimethylethylene chloride piperidium                                                                 0.1                                                    copolymer*.sup.3                                                         (7)  Octyl dodecanol*.sup.4 0.5                                               (8)  Propylene glycol       1.0                                               (9)  Aqueous NaOH solution (48%)                                                                          suitable amount for                                                           adjusting pH to 3.5                               (10) Purified water         balance                                           (11) Propellant (LPG 4.5 kg)                                                                              7.0                                                    Total                  100                                               ______________________________________                                         Note)                                                                         *1: Softanol 90 (Kao)                                                         *2: Yukaformer (Mitsubishi Petrochemical)                                     *3: Merquat 100 (Merck)                                                       *4: Kalcohl 200GD (Kao)                                                  

EXAMPLE 14

A hair foam composition of the following formula was prepared by aroutine method. It had excellent properties in both thefirmness/elasticity of hair fibers and the conditioning effects.

    ______________________________________                                        Formula                 (%)                                                   ______________________________________                                        (1)  2-Naphthalenesulfonic acid . Na                                                                      0.5                                               (2)  95% 8-Acetylated sucrose-modified                                                                    10.0                                                   ethanol                                                                  (3)  Benzyl alcohol         0.5                                               (5)  Amideamino acid triethanolamine (34%)                                                                0.5                                               (6)  Polyoxyethylene-sec-tetradecyl                                                                       0.5                                                    ether (9 E.O.)                                                           (7)  Octyl dodecanol        0.5                                               (8)  Propylene glycol       1.0                                               (9)  Lauryl acrylate . vinyl acetate copolymer                                                            4.0                                                    dispersion (20%)*.sup.1                                                  (10) Vinylpyrrolidone . N,N-dimethylaminoethyl                                                            2.5                                                    methacrylic acid copolymer,                                                   diethyl sulfate*.sup.2                                                   (11) Aqueous NaOH solution (48%)                                                                          suitable amount for                                                           adjusting pH to 3.5                               (13) Purified water         balance                                           (14) Propellant (LPG 4.5 kg)                                                                              7.0                                                    Total                  100                                               ______________________________________                                         Note)                                                                         *1: Polymer ND (Kao)                                                          *2: Gafquat 755N (ISP)                                                   

Industrial Utility

The hair cosmetic composition according to the present invention impartssatisfactory firmness/elasticity to hair fibers in a short time, holdsthe firmness/elasticity for a long time, and provides the hair fiberswith excellent conditioning effects.

We claim:
 1. A hair cosmetic composition which comprises the followingcomponents (A), (B), (C), and (D):(A) an organic solvent, (B) anaphthalene sulfonic acid and/or a benzophenone sulfonic acid, (C) ananionic surfactant and/or an amphoteric surfactant, and (D) an oilyagent,wherein the amounts of the components (A), (B), (C), and (D) are0.5 to 50% by weight, 0.1 to 10% by weight, 0.1 to 25% by weight, and 1to 25% by weight based on the total weight of the composition,respectively.
 2. The hair cosmetic composition according to claim 1,wherein the component (A) is selected from the group consisting ofalkylpyrrolidones having C1-C18 N-alkyl, C1-C4 alkylene carbonates, andthe alcohols represented by the following formula (1): ##STR31## whereinR¹ represents hydrogen, C1-C4 alkyl, or a group ##STR32## (wherein R²represents hydrogen, methyl, or methoxy, R³ represents a direct bond ora C1-C3 saturated or unsaturated divalent hydrocarbon group), Y and Zeach represents hydrogen or hydroxy, p, q, and r are integers of from 0to 5, with the exception of the cases where p═q═r═0 and Z═H; andp═q═r═0, R¹ ═H, and Z═OH.
 3. The hair cosmetic composition according toclaim 1, wherein the component (A) is represented by the followingformula (3): ##STR33## wherein R² is hydrogen, methyl, or methoxy, R³ isa direct bond or a C1-C3 saturated or unsaturated divalent hydrocarbongroup, R⁵ is hydrogen or methyl, s is an integer of from 0 to 5,provided that R³ is not a direct bond if s is
 0. 4. The hair cosmeticcomposition according to claim 1, wherein the component D is selectedfrom the group consisting of C12-C30 saturated alcohols, C12-C30unsaturated alcohols, ethers of these alcohols with polyhydric alcohols,esters of said alcohols with C1-C11 fatty acids, C12-C30 saturated fattyacids, C12-C30 unsaturated fatty acids esters of these fatty acids andmonohydric alcohols, esters of these fatty acids and alcohols, amides ofsaid fatty acids and amines, sterols, squalenes, phospholipids,glycolipids, oils and fats of animal and vegetable origin, andhydrocarbons.
 5. The hair cosmetic composition according to claim 1,wherein the component (D) is a higher alcohol having C12-C26 linear orbranched alkyl or alkenyl.
 6. The hair cosmetic composition according toclaim 1, which further comprises a cationic polymer.
 7. The haircosmetic composition according to claim 6, wherein the cationic polymeris selected from the group consisting of polymers having a unitstructure of dimethyldiallylammonium chloride and copolymers thereof,polymers having a unit structure of methacrylamide alkyl trimethylammonium and copolymers thereof, cationic cellulose, and amino-modifiedsilicone polymers.
 8. The hair cosmetic composition according to claim6, wherein the cationic polymer is selected from the group consisting ofa polymer of dimethyldiallyl ammonium chloride, a copolymer ofdimethyldiallylammonium chloride with acrylate, a copolymer ofdimethyldiallyl ammonium chloride with acrylic amide, a threecomponent-copolymer of dimethyldiallylammonium chloride/acrylicamide/acrylate, a copolymer of dimethyldiallylammonium chloride withhydroxyethylcellulose, a polymer of methacrylamide propyl trimethylammonium, a copolymer of methacrylamide propyl trimethyl ammonium withvinyl pyrrolidone, a copolymer of dimethylaminoethyl methacrylate withvinyl pyrrolidone, and hydroxyethylcellulose-2-hydroxypropyltriethylammonium chloride ether.
 9. The hair cosmetic compositionaccording to claim 1, wherein the pH of the composition is adjusted tofall within a range of from 2 to 5 with a compound capable of forming abuffer system.
 10. The hair composition according to claim 1,wherein:(A) is present in an amount of 2 to 30% by weight; (B) ispresent in an amount of 0.5 to 5% by weight; (C) is present in an amountof 1.0 to 10% by weight; and (D) is present in an amount of 3 to 20% byweight; said % by weight being based on the total weight of thecomposition.
 11. The hair composition according to claim 1, wherein:(A)is present in an amount of 5 to 25% by weight; (B) is present in anamount of 1.0 to 3.0% by weight; (C) is present in an amount of 1.0 to10% by weight; and (D) is present in an amount of 5 to 15% by weight;said % by weight being based on the total weight of the composition.